JPH06279615A - Crystalline thermoplastic resin pillar reinforced with filaments and leaflet inorganic filler - Google Patents

Abstract

PURPOSE:To provide the pillar which can be used as a structural material of high impact strength, low sink deformation and low warpage deformation by allowing inorganic filaments equal length to the pillar and arranged in parallel with the lengthwise direction and a filler of a specific aspect ratio to distribute in the matrix of a crystalline resin. CONSTITUTION:A crystalline thermoplastic resin is quantitatively fed from the first inlet 2 of the extruder 1, leaflet filler of more than 10 aspect ratio such as mica, from the second inlet 3 in an amount of 5 to 15wt.% based on the composite, then they are molten and kneaded, as they are sucked from bent 5, then continuously sent in the impregnation dice 9 at the down-stream end of the extrusion barrel 5. In the meantime, inorganic filaments such as glass fibers are fed from the tank 7 in an amount of 20 to 60wt.% based on the composite, impregnated with molten resin, passed through the cooling water bath 10 and cut by the cutter 11 to obtain the objective crystalline thermoplastic resin pillars which contain inorganic filaments which are arranged in parallel with the pillar direction in the same length as that of the pillars.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a crystalline thermoplastic resin columnar body reinforced with long fibers and a plate-like inorganic filler, and has mechanical strength, particularly impact strength, low sinkability and low warpage in the state of a molded article. The present invention relates to a molding material having excellent deformability and suitable for a structural material.

[0002]

2. Description of the Related Art Various fillers such as glass fiber, carbon fiber, whisker or metal fiber for improving the mechanical strength, rigidity heat resistance deformation and warp deformation property of a crystalline thermoplastic resin molded product. Filler or mica, talc,
Blending plate-like fillers such as glass flakes or kaolinite or granular fillers such as calcium carbonate, diatomaceous earth, alumina or glass beads into a crystalline thermoplastic resin has been conventionally performed and has already been used for a wide range of applications. Is used for.

Among the fillers having various shapes, the fibrous filler has a larger reinforcing effect than the fillers having other shapes. Among them, glass fiber is often used because it is relatively inexpensive and also has excellent cost performance as a reinforcing material, and the crystalline thermoplastic resin columnar body reinforced with glass fiber has mechanical strength, Widely used in fields where rigidity and heat distortion resistance are severe.

As a means for blending a fibrous reinforcing material, glass fiber or carbon fiber (carbon fiber) roving is impregnated with a resin, and then the impregnated product is pultruded and further cut into a predetermined length. The thermoplastic resin columnar pellets reinforced with long fibers by doing so are already known. For example, the following methods can be mentioned.

Japanese Patent Publication No. 52-3985 discloses a method in which a fiber roving is passed through a bed of thermoplastic resin powder, and then the roving is heated to a temperature not lower than the melting point of the resin and extruded from a die to be cut. There is. In this method, a roving is separated into a plurality of filament bundles in a bed of resin powder.

Japanese Unexamined Patent Publication (Kokai) No. 4-27507 discloses that a reinforcing long fiber bundle is passed under tension into a molten thermoplastic resin to impregnate the molten resin into the fiber bundle while the resin is in a molten state. Discloses a method of degassing an impregnated mixture under reduced pressure. The direct effect of this method is to suppress the voids at the interface between the fiber and the resin, that is, to improve the impregnation and wetting of the resin into the fiber, and as a result, mechanical strength such as high tensile strength, bending strength and impact strength. It is said to improve the physical properties.

Industrial Materials 37 , [1] 53-57 (1989) "Cell Strand Properties and Applications" discloses the results of studying the properties of various thermoplastic resins reinforced with long fibers, especially short fiber reinforced ones. Compared with the case, the impact strength is further improved, and the molding shrinkage of the molded product is about the same as that of short fiber reinforced from the relationship between the impact strength and the elastic modulus, and It is mentioned that the deformation is smaller than in the case of short fiber reinforcement.

Synthetic Resin Industry 1990 [4] 102-105 "Special Feature I
In "Progress of Composite Reinforced Plastic Materials and Trend of Application Development", various properties of "glass long fiber reinforced nylon-66" are mainly disclosed under the title "long fiber reinforced resin-Burton-". The effect can be expected to improve both rigidity and toughness,
In particular, it discloses that the impact strength is about twice as high as that in the case of short fiber reinforcement, and also shows that it has an advantage over short fiber reinforcement in mechanical properties in the long term such as creep properties and fatigue properties. . Further, it also discloses that the molded product has less "sink" and relatively less "warpage".

However, none of the above-mentioned prior arts discloses specific conditions for preserving the impact strength of the molded product while eliminating the "warp deformation amount" and the "sink mark deformation amount". Therefore, none of the above-mentioned materials has achieved the same effect as the present invention by defining the shape of the plate-like filler with the same cross section as the condition of the present invention.

The columnar body (abbreviation "LFP") made of a thermoplastic resin composite reinforced with long fibers contains pellets in addition to containing reinforcing fibers of a length equal to the length. Can be molded by a molding machine such as an injection molding machine or an extrusion molding machine equipped with a screw which is a general plasticizing mechanism. Moreover, the thermoplastic resin composite reinforced with long fibers is excellent in lightness as compared with the metal material, and is remarkably improved in strength as compared with the conventional short fiber reinforced composite. This columnar body (LFP) has come to be used as a material for molding a functional component in the fields of automobiles and general machinery by taking advantage of the above advantages.

On the other hand, the plate-like filler and the granular filler independently suppress the warp deformation, but in the effect of improving the tensile strength, bending strength and Izod impact strength as compared with the fibrous filler. Is significantly smaller. However, the plate-like filler, such as mica powder or talc, imparts good rigidity to the crystalline thermoplastic resin molded article. Therefore, an attempt to use a fibrous filler together with the plate-shaped filler has been disclosed in, for example, Japanese Patent Laid-Open No. 52-
It is disclosed in Japanese Patent No. 36141 and Japanese Patent Publication No. 64-11218.

[0012]

Prior art composites reinforced with fibrous fillers consisting only of short fibers are highly suitable for structural materials: low warpage, low sinkability and high resistance to deformation. The impact resistance is insufficient. Moreover, even if the compounding amount of the short fiber filler is increased in order to further enhance the reinforcing effect, the reinforcing effect reaches the upper limit at about 40% by weight.

Further, in the composite disclosed in each of the above-mentioned publications which is reinforced by the combined use of the short fibrous filler and the plate-like filler, the average length of the fibrous filler in the composite finally becomes 0.
In addition to being 2 to 0.5 mm, it is in a region where the compounding amount of the plate-like filler therein is relatively large.

In particular, when the plate-like filler to be mixed is mica (mica), a composite having a compounding amount of 20% by weight or more can be used to obtain a molded product with little warpage and twist deformation. . However, this composite still requires improvement in impact strength and sinkability to be used as a structural material.

However, this LFP has not been sufficiently improved in the low warp deformability, the low twist deformability and the low sink mark deformability, which are strongly required for the structural material. However, their properties are somewhat improved as compared with the thermoplastic resin composite reinforced with short fibers. In that respect, LFP is not yet suitable for use as a material for structural molded articles.

[0016]

Means for Solving the Problems The present inventors have found that the conventional LF
The present invention has been completed as a result of intensive research to solve the above problems remaining in TP. That is, the present invention is a composite of a crystalline thermoplastic resin composite reinforced by blending 20 to 60% by weight of long fibers made of an inorganic material with 5 to 15% by weight of a plate-like inorganic filler having a specific shape. Columnar body (L
FTP: Basic configuration 1) of columnar body.

The columnar body of the present invention may be a mixture of two or more kinds of columnar bodies. That is, a columnar body mixture composed of columnar bodies reinforced with long fibers and columnar bodies reinforced with a plate-like inorganic filler, wherein the long fibers 20 to 60 made of an inorganic material based on the mixture are contained in the columnar body mixture. Those containing 5% by weight and 5 to 15% by weight of the plate-like inorganic filler (basic constitution 2 of the columnar body) are also included in the thermoplastic resin columnar body reinforced with the long fibers and the plate-like inorganic filler of the present invention. .

The effect of the present invention is that the molded product obtained from LFTP retains its excellent impact strength while "the amount of warpage deformation".
And "deformation amount of sink mark" show a significant improvement (any deformation amount is suppressed to a slight value).

The present invention includes the following various aspects. The "columnar body" in the present invention generally has a length (L) / diameter (D).
It is a rod-shaped body having a ratio of 1 or more and a length of 3 to 25 mm. However, the “columnar body” here is not limited to the one having a circular cross section, and includes a flat body, that is, a plate-shaped body. "L" is the length measured in the extrusion direction, and most of the fibers are aligned in this direction in the columnar body. Further, when the columnar body has a flat shape, "D" means not the width but the thickness.

[Basic Structure 1 of Columnar Body] A columnar composite body in which inorganic fibers, practically preferably glass fibers and plate-like fillers, preferably plate-like inorganic fillers, are dispersed in a crystalline thermoplastic resin matrix. The inorganic fibers are contained in an amount of 20 to 60% by weight based on the composite, most of the inorganic fibers are aligned in the longitudinal direction of the columnar body, and have substantially the same length as the columnar body. A long fiber and a plate-like inorganic filler, characterized in that the plate-like inorganic filler has an average diameter of 0.5 to 200 μm and an aspect ratio of 10 or more and is contained in an amount of 5 to 15% by weight based on the composite. Crystalline thermoplastic resin columnar body reinforced with.

[Improved Structure 1 of Columnar Body] The crystalline thermoplastic resin is one or more kinds selected from poly-α-olefin resins, polyester resins, polyamide resins and polyacetal resins, "basic" 1. A crystalline thermoplastic resin columnar body reinforced with the long fibers and the plate-like inorganic filler according to "Structure 1".

[Improved Structure 2 of Columnar Body] The poly-α-olefin resin is a homopolymer of α-olefin and two or more kinds of α-olefins.
"Basic structure 1 of columnar body" and "improved structure of columnar body" characterized by being one or more kinds selected from copolymers of olefins and one or more kinds selected from resin compositions consisting of two or more thereof 1. A crystalline thermoplastic resin columnar body reinforced with the long fibers and the plate-like inorganic filler described in 1).

[Structure 3 for improving columnar body] A homopolymer of α-olefin and a copolymer of two or more types of α-olefin are polyethylene resin, polypropylene resin, poly-1-butene resin, poly-4-methyl- 1-Pentene resin, propylene-
One or more selected from an ethylene copolymer resin and a propylene-1-butene copolymer resin, and one or more selected from a resin composition composed of two or more thereof, "basic columnar body" The crystalline thermoplastic resin columnar body reinforced with the long fibers and the plate-like inorganic filler as described in "Structure 1" and "Columnar improved structure 1" and "Columnar improved structure 2".

[Improved Construction 4 of Columnar Body] Inorganic fibers having an average fiber diameter of 4 to 30 μm and the number of filament bundles 400 to 10
Selected from 000 glass fibers, rock wool, quartz fibers, asbestos fibers and metal whiskers (whiskers) 1
"Basic configuration 1 of columnar body" characterized by being more than one kind
And a crystalline thermoplastic resin columnar body reinforced with long fibers and a plate-like inorganic filler as described in "Columnar improved constitution 1", "Columnar improved constitution 2" and "Columnar improved constitution 3" .

[Improved Structure 5 of Columnar Body] The “basic structure 1 of columnar body” and the “columnar body” are characterized in that the plate-like inorganic filler is one or more selected from mica, talc and glass flakes. Improved structure 1 "," columnar improved structure 2 "," columnar improved structure 3 ", and" columnar improved structure 4 ", and crystalline heat reinforced with long fibers and plate-like inorganic filler Plastic resin columnar body.

[Basic Structure 2 of Columnar Body] A columnar body comprising a composite in which inorganic long fibers are dispersed in a crystalline thermoplastic resin matrix, and most of the inorganic fibers are aligned in the longitudinal direction of the columnar body. And a long-fiber-reinforced columnar body made of a composite having a length substantially the same as the length of the columnar body and a plate-like body made of a composite in which a plate-like inorganic filler is dispersed in a crystalline thermoplastic resin matrix. 20 to 60% by weight of the inorganic long fibers, based on the columnar mixture, in a columnar mixture which is a body-reinforced columnar body and in which the plate-like filler has an aspect ratio of 10 or more and which is substantially composed of the columnar body. Included and the plate-like filler is 5 to 1 on the basis of the columnar mixture.
A crystalline thermoplastic resin columnar mixture reinforced with long fibers and a plate-like inorganic filler, which is characterized by containing 5% by weight.

[Improved Structure 21 of Columnar Body] Long-fiber or plate-like shape characterized in that the crystalline thermoplastic resin is one or more selected from poly-α-olefin resins, polyester resins, polyamide resins and polyacetal resins. The crystalline thermoplastic resin columnar mixture as described in "Basic configuration 2 of columnar body", which is reinforced with the inorganic filler.

[Improved Structure 22 of Columnar Body] The poly-α-olefin resin is selected from one or more kinds selected from homopolymers of α-olefins and copolymers of two or more kinds of α-olefins, and two or more kinds thereof. The crystal according to "basic constitution 2 of columnar body" and "improved constitution 21 of columnar body", which is reinforced with a long fiber and a plate-like inorganic filler, which is one or more kinds selected from the following resin compositions: Thermoplastic resin columnar mixture.

[Improved Structure 23 of Columnar Body] A homopolymer of α-olefin and a copolymer of two or more types of α-olefin are polyethylene resin, polypropylene resin, poly-1-butene resin, poly-4-methyl- One or more selected from a 1-pentene resin, a propylene-ethylene copolymer resin, and a propylene-1-butene copolymer resin, and one or more selected from a resin composition composed of two or more thereof. The crystalline thermoplastic resin columnar body reinforced with the long fiber and the plate-like inorganic filler described in "Basic configuration 2 of columnar body", "Improved configuration 21 of columnar body" and "Improved configuration 22 of columnar body" blend.

[Improved Structure 24 of Columnar Body] Inorganic fibers having an average diameter of 4 to 30 μm and a filament converging number of 400 to 1
“Basic structure 2 of columnar body” and “improved structure 21 of columnar body” to “columnar column”, which is one or more kinds selected from 0000 glass fibers, rock wool, quartz fibers, asbestos fibers and metal whiskers The crystalline thermoplastic resin columnar mixture reinforced with the long fibers and the plate-like inorganic filler according to "Improved Body Structure 24".

[Improved Construction 25 of Columnar Body] The plate-like inorganic filler is selected from mica, talc and glass flakes 1
"Basic configuration 2 of columnar body" characterized by being more than one kind
And "improved structure 21 of columnar body" to "improved structure 2 of columnar body 2"
[4] A mixture of crystalline thermoplastic resin columns reinforced with long fibers and a plate-like inorganic filler.

[Crystalline Thermoplastic Resin Matrix] As the resin for the crystalline thermoplastic resin matrix constituting the crystalline thermoplastic resin columnar body (LFTP) reinforced with the long fiber and the plate-like inorganic filler of the present invention, The following can be exemplified: Poly-α-olefin resin: polyethylene resin, polypropylene resin, poly-1-butene resin, poly-4-methyl-1-
One or more of pentene resin, propylene-ethylene copolymer resin and propylene-1-butene copolymer resin; Polyester resin: one or more of polyethylene terephthalate, polybutylene terephthalate and polyethylene terephthalate isophthalate; Polyamide resin (nylon) ): Polyamide-6, Polyamide-7, Polyamide-66, Polyamide-610, Polyamide-
11 and polyamide-12; -polyacetal; -polyurethane; -composition comprising two or more of the above and polymer alloy comprising two or more.

When the resin does not have a reactive functional group or a polar functional group for imparting interfacial adhesiveness to an inorganic fiber, particularly a glass fiber, at the molecular end like a polyolefin (poly-α-olefin), the resin is It is useful to take measures such as modifying with an unsaturated acid or a derivative thereof such as an acid anhydride, and / or adding a necessary amount of a polymer modified with an unsaturated acid to an unmodified resin.

[Resin Modifying Agent] The unsaturated acid that can be used as the above modifying agent is usually an aliphatic unsaturated acid and is selected from, for example, acrylic acid, methacrylic acid, maleic acid, citraconic acid and mesaconic acid. One or more, preferably maleic acid.

Derivatives such as unsaturated acid anhydrides that can be used as modifiers are usually aliphatic unsaturated acid anhydrides, and are selected from, for example, maleic anhydride and itaconic anhydride.
More than one species, and preferably maleic anhydride (maleic anhydride).

[Inorganic fiber] Columnar body (LFTP) of the present invention
As the inorganic fibers constituting the, those formed from various inorganic materials can be used. The inorganic fibers may be, for example, glass fibers, rock wool, asbestos, quartz fibers, metal fibers, whiskers and carbon fibers. Among them, glass fiber is usually used because of its properties and availability. This glass fiber is a glass roving that is usually manufactured and marketed for resin reinforcement, and usually has an average fiber diameter of 4 to
The average fiber diameter is 30 to 30 μm, the number of filament bundles is 400 to 10,000, and the Tex count is 300 to 20,000, and the average fiber diameter is preferably 9 to 23 μm. If necessary, these glass rovings may be combined and used.

It is preferable that the surface of the plate-like inorganic filler constituting the columnar body of the present invention is subjected to some treatment especially for imparting or improving the interfacial adhesion to the matrix resin.

[Plate-like Inorganic Filler] The plate-like inorganic filler constituting the columnar body (LFTP) of the present invention is not particularly limited as long as it is an inorganic plate-like body satisfying the following shape characteristics, and it is widely used. You can choose from different types. Normally,
One or more of mica, talc, glass flakes and the like can be selected and used according to the application. Of these, the preferred plate-like filler is mica.

[Shape characteristics of plate-like inorganic filler] The plate-like filler constituting the columnar body of the present invention has an average diameter of plate-like crystals of usually 0.5 to 200 µm, preferably 1 to 100 µm.
The ratio of the average diameter (D) to the average thickness (T) (D / T: average aspect ratio) is usually 10 or more, preferably 12 to 40. A plate-like filler having an average aspect ratio of 8 or less cannot exhibit a sufficient "warp deformation suppressing effect" and "sink deformation suppressing effect" for a molded product formed of a columnar body.

Here, the "average diameter" is the arithmetic mean value of the maximum diameter and the minimum diameter, and the average thickness is the arithmetic mean value of the maximum thickness and the minimum thickness. [Surface Characteristics of Plate-shaped Inorganic Filler] The surface of the plate-shaped inorganic filler constituting the columnar body of the present invention may be subjected to some treatment in order to impart or improve interfacial adhesion to the matrix resin. preferable.

[Production of LFTP] The composite material for producing the long-fiber-reinforced crystalline thermoplastic resin columnar body (LFTP) of the present invention can be produced, for example, by the following procedure: [Based on the drawings Description] Hereinafter, description will be given with reference to FIG. 1: A predetermined amount of each of the crystalline thermoplastic resin for the matrix and the plate-like inorganic filler was charged into a Henschel mixer (trade name; not shown) and mixed with stirring. After that, the mixture is supplied from the first raw material supply port 2 of the extruder 1 to a temperature of 150 to 3
Melt and knead at 00 ° C. The extruder 1 may be a single screw type or a twin screw type.

Next, the melt-kneaded product is merged with the glass roving 8 separately supplied from the glass roving raw material 7 in the impregnating die 9 mounted at the downstream end of the extrusion barrel 6 of the extruder 1 to make the glass roving 8 Impregnating a molten resin matrix and a plate-like filler between each monofilament of,
The die 9 is extruded in a strand shape. The strand is introduced into the cooling tank 10, cooled to room temperature with water, and then cut into a columnar body (LFTP; pellet) by a strand cutter 11 to have a length of about 3 to 20 mm. Extruder using only crystalline thermoplastic resin for matrix 1
Supply from the first raw material supply port 2 (normal raw material supply port) of
The plate-like inorganic filler is supplied from the second raw material supply port 3 of the extruder 1 and melt-kneaded at the same temperature. The extruder A may be a single screw type or a twin screw type.

Next, the melt-kneaded product is merged with the glass roving 8 separately supplied from the glass roving raw material 7 in the impregnating die 9 mounted at the downstream end of the extrusion barrel 6, and each monofilament of the glass roving 8 is joined. A molten resin matrix and a plate-like filler are impregnated between them and extruded from the die 9 in a strand form. Cool the strand 1
0 and then cooled to room temperature with water, and then cut with a strand cutter 11 to a length of about 3 to 20 mm to form a columnar body (LFT).
P; pellet) is prepared. Extruder using only crystalline thermoplastic resin for matrix 1
Supply from the first raw material supply port 2 (normal raw material supply port) of
Melt at the same temperature as in. The extruder 1 may be a single screw type or a twin screw type.

Next, the melt is placed in an impregnating die 9 attached to the downstream end of the extruder barrel 6 to obtain a glass roving original 7
The glass roving 8 separately supplied from the above is merged to impregnate the molten resin matrix between the monofilaments of the glass roving, and extruded in a strand form from the die 9. The strand is introduced into the cooling tank 10 and is cooled to room temperature with water, and then the length is about 3
A columnar body (LFP; pellet) is produced by cutting into 20 mm.

A crystalline thermoplastic resin columnar body (LFP) reinforced only by the long glass fibers and a separately prepared plate-like inorganic filler reinforced crystalline thermoplastic resin columnar body (TP) are prepared. For example, dry blending.

[Other Additives] The columnar body (LFT) of the present invention
If desired, one or more of the following various additives may be added to the composite constituting P):-Antioxidant, heat stabilizer, UV absorber, resinous breakage preventive agent, antistatic agent. Agents, lubricants, plasticizers, mold release agents, flame retardants (flame retardants), flame retardant aids and crystallization accelerators (nucleating agents; crystallization nucleating agents), dyes and pigments, etc.

These additives may be used in the form of being pre-blended with the above-mentioned crystalline thermoplastic resin which serves as a matrix, or may be used in the form of a masterbatch. [Production of molded product] When a molded product is produced using the FLTP of the present invention, various molding machines can be used as a molding means. In this case, the point to be noted is to select a condition that does not reduce the openability of the reinforcing fiber at the time of molding and does not cause breakage of the reinforcing fiber, which is specifically as follows: Select a low compression ratio screw (avoid high compression ratio screw) ・ Mold at low screw rotation speed ・ Mold at low injection speed ・ Choose conditions that do not apply back pressure ・ Nozzle diameter and structure and gate diameter And select the structure.

[0048]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the scope of the present invention is not limited thereto.

As a test method for evaluating the effect of the present invention, surface impact strength, warp deformation amount and sink mark deformation amount were measured as follows: * Surface impact strength: Square flat plate (vertical 50 mm × width) 50 mm × 2 mm thick) A test piece is prepared. Manufacturing conditions: Injection pressure is set to 30 by side gate.
It was controlled to be 0 kgf / cm ² . The obtained rectangular flat plate was placed under the conditions of a temperature of 23 ° C. and an RH of 50% for 48 hours for conditioning.

Next, the impact tester [Dynatup Impact Test
Machine GRC 82501 GRC730-I (manufactured by General Research Co.)] was installed with a test piece to perform a surface impact test. The total amount of energy (kg-cm) observed was defined as the surface impact strength.

Measurement conditions: tap diameter 1 / 2''R, pedestal (diameter)
1.5 '', hammer weight 2.9 kgf, height 1 m, drop speed 4 m / sec, temperature 23 ° C. * Warp deformation: A circular flat plate (diameter 150 mm x thickness 2 mm) is prepared. Manufacturing conditions: The injection pressure was controlled by a direct gate so that the internal pressure was 300 kgf / cm ² . The obtained circular flat plate was placed under the conditions of a temperature of 23 ° C. and an RH of 50% for 48 hours for conditioning.

Next, the test piece is fixed on a horizontal table, and the distance from the horizontal plane is measured as "warp deformation amount". Different amounts of deformation are observed depending on different fixed positions. In order to cope with this variation, the fixed position of the test piece is changed variously to measure each “warp deformation amount”, and the maximum value is defined as the “warp deformation amount” (unit: mm). * Deformation of sink mark: A flat plate with ribs (see Fig. 2) is prepared. Test piece shape: (Substrate: BB) Vertical 150 mm × Horizontal 50 mm
× thickness 3 mm × (rib: RB) height 20 mm × rib width 2 mm.
A curvature R is provided on the line of intersection (CL) between the rib RB and the substrate BB. Manufacturing conditions: Injection pressure is 300 by internal pressure by side gate
It was controlled to be kgf / cm ² . The obtained flat plate with ribs was placed under the conditions of a temperature of 23 ° C. and a RH of 50% for 48 hours for conditioning.

Next, the test piece was fixed to the tracer CA-42 by hanging the rib, and the depth of the recess formed at the position facing the rib on the substrate was measured and defined as the "sinker deformation amount" (unit: : μm). * Preparation conditions of polyamide resin mixture: Resin mixture 1: unmodified polypropylene resin (homopolymer) [MFR (230 ℃; 2.16kgf) 2g / 10min] 99.20% by weight of powder, not a modifier Maleic anhydride as a saturated acid.
5% by weight, 0.13% by weight of 1,3-bis (t-butylperoxyisopropyl) benzene as an organic oxide, and 0.1% by weight of 2,6-di-t-butyl-p-cresol as an antioxidant. And, a mixture of 0.1% by weight of calcium stearate as a lubricant was stirred and mixed in a Henschel mixer (trade name; not shown).

The resin mixture is supplied as the extruder 1 from the first supply port 2 of a twin-screw extruder (diameter 45 mm; L / D30; plural raw material supply ports are installed), melt-kneaded at a temperature of 200 ° C., and then extrusion granulated. did. The modified polypropylene (PP) obtained is M
It had an FR of 130 g / 10 min and a modifier graft ratio of 0.3%. -Resin mixture 2: Nylon-6 [MFR110g / 10min (Toray)], mica (mica; aspect ratio 20), talc [aspect ratio 12 (Hayashi Kasei)] and glass flake [aspect ratio 35 (Nippon Sheet Glass) Company)].

[0055]

Example 1 A resin mixture 1 (57% by weight) was quantitatively supplied from a first supply port 2 of an extruder 1, and mica (13% by weight) was quantitatively supplied from a second supply port 3 while being sucked from a vent 5. After being melt-kneaded, it is continuously fed into the impregnating die 9 mounted at the downstream end of the extrusion barrel 6. On the other hand, while supplying the glass roving a8 from the glass roving original fabric 7 to the impregnation die 9, a composite in which the molten resin was sufficiently impregnated between the monofilaments of the glass roving was extruded in a strand shape. Here, as the glass roving a, the average fiber diameter is 17 μm, the number of filaments is 4000, and the Tex count is 2
At 310, one for polypropylene was used.

The extruded strand is cooled to normal temperature with water in the cooling tank 10, and the length of the strand is reduced to about 1 by the strand cutter 11.
A columnar body (LFTP) was produced by cutting it to 0 mm. The columnar body was set so as to contain 30% by weight of glass fiber based on the whole.

The obtained columnar body was loaded into an injection molding machine to mold a predetermined test piece (resin temperature: 250 ° C., mold temperature: 50).
℃), and subjected to various evaluation tests. The results are shown in Table 1.

[0058]

[Comparative Example 1] Resin mixture 1 from first feed port 2 of extruder 1
(70% by weight) is supplied, melted and kneaded from the vent 5 under suction, and then continuously supplied to the impregnating die 9. On the other hand, while supplying the glass roving a8 to the impregnation die 9, a composite in which the molten resin was sufficiently impregnated between the monofilaments of the glass roving was extruded in a strand form.

Thereafter, the extruded strand was cut into a length of 10 mm in the same manner as in Example 1 to prepare a columnar body (LFP; pellet). The columnar body was set so as to contain 30% by weight of glass fiber based on the whole.

The obtained columnar body was put into an injection molding machine, and predetermined test pieces were molded in the same manner as in Example 1 and subjected to various evaluation tests. The results are also shown in Table 1.

[0061]

[Comparative Example 2] Resin mixture 1 from first feed port 2 of extruder 1
(55% by weight), 15% by weight of mica (the same as in Example 1) from the second supply port 3, and glass fiber b (chopped strand having an average fiber diameter of 13 μm) 3 from the third supply port 4.
0 wt% of each was quantitatively supplied, and the composite formed after melt-kneading from the vent 5 under suction was extruded in a strand shape.

Thereafter, the extruded strands were cut into a length of 3 mm in the same manner as in Example 1 to prepare columnar bodies (SFTP; pellets). The columnar body was set so as to contain 30% by weight of glass fiber based on the whole.

The obtained columnar body was put into an injection molding machine, and a predetermined test piece was molded in the same manner as in Example 1 and subjected to various evaluation tests. The average fiber length of the residual glass fibers in the ash produced by steam-baking (600 ° C. × 2 h) a part of the obtained columnar body was 0.4 mm. Table 1 for both results
Are also shown.

[0064]

[Comparative Example 3] Resin mixture 1 from first feed port 2 of extruder 1
(45% by weight), 25% by weight of mica (same as that of Example 1) from the second supply port 3, and glass fiber b (30% by weight) from the third supply port 4 in a fixed amount, and a vent 5 The composite formed after melt-kneading under suction was extruded into a strand.

Thereafter, the extruded strand was cut into a length of 3 mm in the same manner as in Example 1 to prepare a columnar body (LFTP; pellet). The columnar body was set so as to contain 30% by weight of glass fiber based on the whole.

The obtained columnar body was put into an injection molding machine, and predetermined test pieces were molded in the same manner as in Example 1 and subjected to various evaluation tests. In addition, a part of the obtained columnar body was used as a comparative example 2.
The average fiber length of the glass fibers remaining after the same treatment as in (3) was 0.35 mm. Both results are also shown in Table 1.

[0067]

[Comparative Example 4] Resin mixture 1 from first feed port 2 of extruder 1
(60% by weight), and mica (the same as in Example 1; 40% by weight) were quantitatively supplied from the second supply port 3 and melt-kneaded from the vent 5 under suction to form a composite formed into a strand. Extruded into a shape.

Thereafter, the extruded strand was cut into a length of 3 mm in the same manner as in Example 1 to prepare a columnar body (pellet). The obtained columnar body was put into an injection molding machine, and a predetermined test piece was molded in the same manner as in Example 1 and subjected to various evaluation tests.

[0069]

[Examples 2 and 3 and Comparative Example 5] In each of the experimental examples, injection molding was carried out with the following respective formulations to prepare predetermined test pieces, which were then subjected to various evaluation tests. The results are also shown in Table 1.

Formulation of Example 2: Resin mixture 1 (60% by weight), Mica (identical to that of Example 1; 10% by weight) and glass fiber a (30% by weight); Formulation of Example 3: Resin mixture 1 (63% by weight), mica (same as in Example 1; 7% by weight) and glass fiber a
(30% by weight); Formulation of Comparative Example 5: Resin mixture 1 (50% by weight), Mica (same as in Example 1; 20% by weight) and glass fiber a (30% by weight).

[0071]

[Examples 4 and 5 and Comparative Examples 6 and 7] In each of the experimental examples, injection molding was performed according to the following respective formulations to prepare predetermined test pieces, which were subjected to various evaluation tests. The results are also shown in Table 1.

Formulation of Example 4: Resin mixture 1 (70% by weight), Mica (identical to that of Example 1; 10% by weight) and glass fiber a (20% by weight); Formulation of Example 5: Resin mixture 1 (30% by weight), mica (same as in Example 1; 10% by weight) and glass fiber a (15% by weight); Formulation of Comparative Example 6: Resin mixture 1 (75% by weight), Mica (Example) Same as 1; 10% by weight) and glass fiber a (15% by weight).

Formulation of comparative example 7: resin mixture 1 (20% by weight), mica (same as in example 1; 10% by weight) and glass fiber a (70% by weight).

[0074]

EXAMPLE 6 AND COMPARATIVE EXAMPLE 8 Strands were prepared with the same formulation using resin mixture 1, mica and glass fibers as in Example 1 as a common composite.

Columnar body of Example 6 (LFTP): a strand of the common composite cut to a length of 5 mm; Columnar body of Comparative Example 8 (SFTP): a strand of the common composite cut to a length of 2 mm .

Injection molding was carried out in the same manner as in Example 1 using the respective columnar bodies, and predetermined test pieces were produced. These test pieces were subjected to various evaluation tests. The results are shown in Table 1.

[0077]

[Examples 7 and 8] In Example 7, talc was used as the plate-like filler, and in Example 8, the same amount of resin mixture 1 and glass fiber a as in Example 2 was used except that glass flakes were used as the plate-like filler. A composite is formed using the same method as in Example 1, and these are cut to form a columnar body (LFT).
P) was prepared.

Predetermined test pieces were prepared by injection-molding each of these columnar bodies and subjected to various evaluation tests. The results are shown in Table 2.

[0079]

Example 9 A columnar body (LFTP) was prepared in the same manner as in Example 1 except that the resin mixture 2 and the glass fiber c were used, and the same amount of mica as in Example 1 was used.
Was produced. Here, as the glass fiber c, the average fiber diameter is 13 μm, the number of filaments is 4000, and the Tex count is 2.
In 310, one for polyamide was used.

The obtained columnar body was injection-molded (resin temperature 280 ° C .; mold temperature 80 ° C.) to prepare a predetermined test piece for evaluation. This test piece was subjected to various evaluation tests. The results are shown in Table 2.

[0081]

Comparative Example 9 A columnar body (SFTP) was produced in the same manner as in Comparative Example 2 using the same amount of mica as in Comparative Example 2 except that the resin mixture 2 and the glass fiber d were used. Here, the average fiber diameter of the glass fibers d is 13 μm.
m chopped strands were used.

The obtained columnar body was injection-molded in the same manner as in Example 9 to prepare a predetermined test piece for evaluation.
This test piece was subjected to various evaluation tests. The results are shown in Table 2.
Shown in.

[0083]

Comparative Example 10 The same amount of mica as in Example 1 was used except that the resin mixture 2 and the glass fiber c were used.
A columnar body (LFTP) was prepared in the same manner as in Example 1.

Using the obtained columnar body, injection molding was performed in the same manner as in Example 9 to prepare a predetermined test piece for evaluation. This test piece was subjected to various evaluation tests. The results are shown in Table 2.

[0085]

Example 10 Resin mixture 1 (57% by weight) was added to extruder 1
A fixed amount is supplied from the first supply port 2, and the mixture is melted and kneaded from the vent 5 under suction, and then continuously supplied into the impregnation die 9 attached to the downstream end of the extrusion barrel 6. On the other hand, while supplying the glass roving a8 to the impregnation die 9, a composite in which the molten resin was sufficiently impregnated between the monofilaments of the glass roving was extruded in a strand shape. Here, as the glass roving a8, one having an average fiber diameter of 17 μm, the number of filaments of 4000, and Tex count 2310 for polypropylene was used.

Thereafter, the extruded strand was cut into a length of 10 mm in the same manner as in Example 1 to prepare a columnar body (LFP; pellet). The columnar body was set so as to contain 60% by weight of glass fiber based on the whole. The columnar body (LFP) and a columnar body (TP) separately prepared, which is a columnar body and does not contain long fibers and contains 26% by weight of mica, is 1 based on the weight.
Dry blending was carried out in a ratio of 1 to obtain a columnar body mixture having a glass fiber content of 30% by weight and a mica content of 13% by weight on the basis of the columnar body mixture.

The columnar blend thus obtained was charged into an injection molding machine in the same manner as in Example 1 to form a predetermined test piece, and subjected to various evaluation tests. The results are shown in Table 2. [Observation of Evaluation Results] (1) The test piece in Example 1 using the columnar body (LFTP) of the present invention was a columnar body (LF) containing only glass fibers.
The amount of warp deformation and the amount of sink mark deformation significantly improved as compared with the test piece of Comparative Example 1 using P). -The test piece in Example 1 using the columnar body (LFTP) of the present invention is significantly improved in surface impact strength and "depression deformation amount" as compared with the test piece in Comparative Example 4. -The test piece of Comparative Example 4 contained mica 40 without glass fiber blending.
Only the weight% was compounded, and the test piece of Example 1 was equivalent in terms of "warp deformation amount". The test piece in Example 1 using the columnar body (LFTP) of the present invention is significantly improved in surface impact strength and “sinker deformation amount” as compared with the test piece in Comparative Example 2. -The test piece in Comparative Example 2 was prepared by selecting the compounding amount of the plate-like filler in the low compounding amount region within the scope of the claims of the present invention, and the "warpage deformation amount" was improved as much as in Example 1. It has not been. The test piece in Comparative Example 3 was manufactured from a columnar body (SFPT) containing short glass fibers and mica, and with a mica content of 25% by weight, a low “warpage” substantially equal to that of the test piece of Example 1 was obtained. The amount of deformation ”is shown. (2) When comparing the necessary amounts of mica with respect to the amount of glass fiber (30% by weight) in comparison with Examples 2 and 3 and Comparative Example 5, the following matters become clear: ・ Mixing amount of mica 7 Although significant improvements in "warp deformation amount" and "sink mark deformation amount" are seen at 10% by weight and 10% by weight, they are not as high as those in Comparative Example 5. -In "surface impact strength", it far exceeds that of Comparative Example 5. (3) When the compounding amount of glass fiber to the compounding amount (10% by weight) of mica is compared with Examples 4 and 5 and Comparative Examples 6 and 7, the following matters become clear: "Amount of surface impact", "Amount of warp deformation" and "Amount of sink mark" at 20% by weight and 60% by weight
A significant improvement can be seen in. -"Glass deformation amount" and "surface impact strength" when the glass fiber content is 15% by weight (Comparative Example 5).
In either case, it is insufficient. -With a glass fiber content of 70% by weight (Comparative Example 7), granulation was impossible (columnar body could not be prepared). (4) In Example 6 and Comparative Example 8, the criticality is shown when glass fibers having a short average fiber length are present in the columnar body. The length of glass fiber in these examples is shorter than the length in the examples. -In the average glass fiber length of 5 mm (Example 6), the "surface impact strength", "warp deformation amount" and "sink deformation amount" were all improved. -In an average glass fiber length of 2 mm (Comparative Example 8), all of "surface impact strength", "warp deformation amount" and "sink mark deformation amount" are insufficient. (5) In Examples 7 and 8, a test piece containing talc or glass flakes instead of the mica in Example 2 was used as the plate-like filler. -In both examples, "surface impact strength", "warp deformation amount"
Also, the "deformation amount of sink mark" is improved in the same manner as in the first embodiment. (6) In Example 9 and Comparative Examples 9 and 10, a test piece containing polyamide-6 as a crystalline thermoplastic resin was used. -In Example 9, the "warp deformation amount" and the "sink mark deformation amount" are significantly improved as compared with Comparative Example 10 (comprising only glass fiber as the filler). -In Comparative Example 9, a test piece containing short glass fibers was used, and almost all of "surface impact strength", "warp deformation amount" and "sink deformation amount" were improved unlike Example 9. It has not been. (7) In Example 10, the following columnar body (A) and columnar body (B)
A test piece made from a columnar body blend (LFP + TP) by a dry blending of 1: 1 by weight ratio was used. The columnar blend contained the same amounts of mica and glass fibers as in Example 1. Columnar body (A): Columnar body (LFP) containing 60% by weight of glass fiber without mica Columnar body (B): Columnar body containing 26% by weight of mica without long fiber (T
P) ・ “Surface impact strength”, “Warp deformation amount” and “Sink deformation amount”
In any of these cases, the improvement was the same as in Example 1. (8) In Example 11, polyamide (nylon) -66 was used as the crystalline thermoplastic resin, and glass flakes (aspect ratio 35) were blended as the plate-like inorganic filler. Although the "warp deformation amount" and the "depression deformation amount" were larger than those in Example 1 by the same level as in No. 1, it was improved to a level where practically no problem occurs. (9) In Example 12, polyamide (nylon) -66 was used as the crystalline thermoplastic resin, and the same mica as in Example 1 was used as the plate-like inorganic filler, so that the amount of warpage deformation was increased. "And the amount of sink mark deformation" to the same level as in Example 1, and further "surface impact strength"
In Example 1, the effect was improved to a level exceeding the effect in Example 1 by 10%.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

INDUSTRIAL APPLICABILITY The crystalline thermoplastic resin columnar body (LFTP) reinforced with the long fiber and the plate-like inorganic filler of the present invention is reinforced only with the columnar body reinforced only with the long fiber and the plate-like inorganic filler. (Includes columnar mixture consisting of columns)
The molded product produced from was significantly improved in all of "surface impact strength", "warp deformation amount" and "sink deformation amount". As a result, the LFTP of the present invention can finally be used for structural materials.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional process diagram of an LFTP manufacturing apparatus of the present invention, in which an impregnation die is attached to the downstream end of the extruder.

FIG. 2 is a perspective view of a ribbed flat plate-shaped test piece used for measuring a “depression deformation amount” of a molded article produced from the LFTP of the present invention.

[Explanation of symbols]

 1 Extruder 2 First Feeding Port for Forming Raw Material 3 Second Feeding Port for Forming Raw Material 4 Third Feeding Port for Forming Raw Material 5 Suction Vent 6 Extrusion Barrel 7 Glass Roving Raw Fabric 8 Glass Roving 9 Impregnation Die 10 Cooling Tank 11 Strand Cutter BB Substrate of sink mark measurement specimen CL Crossing line between substrate of sink mark measurement specimen and rib RB Rib of sink mark measurement specimen

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08L 101/00

Claims (12)

[Claims] 1. A columnar body comprising a composite in which an inorganic long fiber and a plate-like inorganic filler are dispersed in a crystalline thermoplastic resin matrix, wherein the inorganic fiber is 20 to 20 on a composite basis.
60% by weight of each of the inorganic fibers are aligned in the longitudinal direction of the columnar body and have substantially the same length as the columnar body, and the plate-like filler has an aspect ratio of 10 or more. A crystalline thermoplastic resin columnar body reinforced with long fibers and a plate-like inorganic filler, characterized in that the content is 5 to 15% by weight based on the composite. 2. The long fiber and plate of claim 1, wherein the crystalline thermoplastic resin is one or more selected from poly-α-olefin resins, polyester resins, polyamide resins and polyacetal resins. The crystalline thermoplastic resin columnar body reinforced with the inorganic filler. 3. The poly-α-olefin resin is selected from one or more selected from homopolymers of α-olefins and copolymers of two or more α-olefins, and a resin composition comprising two or more thereof. The crystalline thermoplastic resin columnar body reinforced with the long fibers and the plate-like inorganic filler according to claim 1 or 2, characterized in that 4. An α-olefin homopolymer and a copolymer of two or more α-olefins are polyethylene resin, polypropylene resin, poly-1-butene resin, poly-4-methyl.
1-pentene resin, propylene-ethylene copolymer resin and propylene-1-butene copolymer resin 1
It is 1 or more types selected from the resin composition which consists of 1 or more types and those 2 or more types, It is characterized by the above-mentioned.
A crystalline thermoplastic resin columnar body reinforced with the long fiber and the plate-like inorganic filler according to any one of 1. 5. The inorganic fiber is one or more selected from the group consisting of glass fibers having an average fiber diameter of 4 to 30 μm and a filament converging number of 400 to 10,000, rock wool, quartz fiber, asbestos fiber and metal whiskers. A crystalline thermoplastic resin columnar body reinforced with the long fiber according to any one of claims 1 to 4 and a plate-like inorganic filler. 6. The long fiber and the plate-like inorganic filler according to claim 1, wherein the plate-like inorganic filler is one or more kinds selected from mica, talc and glass flakes. Reinforced crystalline thermoplastic resin column. 7. A columnar body composed of a composite in which inorganic long fibers are dispersed in a crystalline thermoplastic resin matrix,
A long fiber reinforced columnar body composed of a composite in which most of the inorganic fibers are aligned in the longitudinal direction of the columnar body and having a length substantially the same as the length of the columnar body, and a plate in a crystalline thermoplastic resin matrix In a columnar body-reinforced columnar body comprising a composite in which a plate-like inorganic filler is dispersed, wherein the plate-like filler is substantially composed of columnar bodies having an aspect ratio of 10 or more. 20 to 60% by weight of the inorganic long fibers based on the mixture of columnar bodies and 5 to 15% by weight of the plate-like filler based on the mixture of the columnar bodies are contained, and long fibers and plate-like inorganics A crystalline thermoplastic resin column mixture reinforced with a filler. 8. The long fiber and plate of claim 7, wherein the crystalline thermoplastic resin is one or more selected from poly-α-olefin resins, polyester resins, polyamide resins and polyacetal resins. A mixture of crystalline thermoplastic resin columns reinforced with the inorganic filler of. 9. The poly-α-olefin resin is selected from one or more kinds selected from homopolymers of α-olefins and copolymers of two or more kinds of α-olefins, and resin compositions composed of two or more kinds thereof. The crystalline thermoplastic resin columnar mixture reinforced with the long fibers and the plate-like inorganic filler according to claim 7 or 8, characterized in that it is one or more types. 10. An α-olefin homopolymer and a copolymer of two or more α-olefins are polyethylene resins,
One or more selected from polypropylene resin, poly-1-butene resin, poly-4-methyl-1-pentene resin, propylene-ethylene copolymer resin and propylene-1-butene copolymer resin, and two or more thereof. It is 1 or more types chosen from the resin composition consisting of.
9. A crystalline thermoplastic resin columnar mixture reinforced with the long fiber and the plate-like inorganic filler according to any one of 9 above. 11. The inorganic fiber is one or more selected from glass fibers having an average diameter of 4 to 30 μm and 400 to 10,000 filament bundles, rock wool, quartz fibers, asbestos fibers and metal whiskers. Item 11. A crystalline thermoplastic resin columnar mixture reinforced with the long fiber according to any one of items 7 to 10 and a plate-like inorganic filler. 12. The long fiber and the plate-like inorganic filler according to claim 7, wherein the plate-like inorganic filler is one or more kinds selected from mica, talc and glass flakes. Reinforced crystalline thermoplastic resin column mixture.